Lube additives made by solvent refining high molecular weight aliphatic-aromatic condensation products



Patented Nov. 23, 1948 UNITED smes orrlca I Lona inmmes fiz n-so mr as QQ ING HIGH -MOLECULAB WEIGHT A il IPHATIC-AROMATIC CONDENSATIO PRODUCTSCaleb E. Hodges, Roselle, N. 3., and Aioyliua F. Cashman, Staten Island,N. Y.,-aaslgnora to Standard Oil Development Company, a corporation oiDelaware No Drawing. Application September-'19, 194.6,

" Serial No. 697,920

hydrolyzing agent, settling and removing the sludge and distilling thereaction products under it relates to an improved method of refining orI finishing a Friedel-Crafts condensation product which is particularlyuseful as an addition agent in waxy mineral lubricationg oils since ithas both the property of reducing and pour point of such oils and alsoof improving the viscosity index thereof.

It is already known according to U. S. Patent 1,815,022 and others suchas 2,174,246 that chlorinated paraflin wax can be condensed withnaphthalene to make high molecular weight condensation products whichhave pour depressing properties, however, such products as generallyheretofore made, do not have any viscosity indeximproving property.

The type of condensation product to which the invention is foundparticularly applicable is that made according to U. S. Patent2,339,493, and obtained by condensing a halogenated high molecularweight aliphatic material having more than carbon atoms with an aromaticcompound by mixing together the aromatic compound, a Friedel-Craftscatalyst and a low molecular weight halogenated hydrocarbon solventinert under the reaction conditions used, adding the halogenated highmolecular weight aliphatic hydrocarbon of at least halogen content, andmaintaining the mixture at a reaction temperature until the reaction iscompleted, the arithmetical product of the percent of catalyst (based onthe weight of halogenated high molecular weight aliphatic material),times the square of the percent by weight of halogen in the halogenatedhigh molecular weight aliphatic material being at least 400. Thisprocess is typified by mixing together naphthalene, aluminum chlorideand tetrachlorethane and adding thereto chlorinated paraflin waxcontaining about 25% chlorine, using about 3-8 mols of chlorinated waxper mol of naphthalene, about 1-3% of aluminum chloride based on thechlorinated wax and about -100 volumes of tetrachlorethane per 100volumes of chlorinated wax, and maintaining the reaction mixture at atemperature between the approximate limits of 70-150" F. for a reactiontime of about 1 to 5 hours, subsequently treating the reaction mixturewith a reduced pressure,- e. g.. by vacuum or iire and steamdistillation, to a temperature of at least 400- F. or somewhat higher toobtain as distillation residue the desired wax-naphthalene condensationproduct having both pour-depressing and V. I.-improving properties. If,as is generally the case, the product is intended to be used as alubricating oil additive, it is desirable to add a small amount of arefined lubricating oil basestock before removing the volatile solventin the above mentioned final distillation step.

For the sake of simplicity, this type of condensation product will bereferred to as Product A.

One difllculty which has been experienced in the refining or recovery ofProduct A is that it is difficult to remove all of thechlorine-containing compounds, which may consist of residual chlorinatedhydrocarbon solvent or of condensation products of naphthalene withchlorinated wax in which only part of the chlorine had reacted and beenremoved. The residual chlorine content has in several instances rangedfrom about 8 to 15% by weight based on the condensation product per se,or about 3 to 6% by weight based on the oil blend obtained when thecondensation product is recovered in the presence of some lubricatingoil added prior to the removal of volatile solvent by distillation.While for use in certain fields the presence of a small amount oftetrachlorethane or other relatively inert chlorinated hydrocarbonliquid or condensation product containing some residual chlorine willnot be objectionable, in other cases it is desirable to remove suchtraces as completely as possible from the product.

Accordingly it is one object of this invention to remove residual tracesof halogenated hydrocarbon solvent from Product A type of condensationproducts. Another object of the invention is to prepare suchcondensation products which are substantially free of halogen, i. e.,which have less than about 6%, preferably less than about 4%, based onthe refined condensation product per se, or less than 2% and preferablyless than 1% of halogen on the basis of the oil blend, and which areaccordingly safer to use in applications where the presence ofhalogenated hydrocarbons might tend to cause corrosion of metals orother undesirable results.

These and other objects and advantages will appear more fully from thefollowing description and examples.

Broadly, the invention comprises solvent-extraction Product A with asuitable solvent for halogenated hydrocarbon liquids.

The liquid to be used as solvent for this solvent extraction accordingto the present invention is preferably an organic liquid containinghydrogen and carbon and at least one other element and is preferably anorganic liquid having preferential solvency for halogenated hydrocarbonliquid in preference to aliphatic or aryl-aliphatic hydrocarbons, suchas materials selected from the following general classes, in which oneor more specific examples are given for the sake of illustration.

Also, if desired, mixtures of two or more of these various solvents maybe used, and the solvent extraction may, if desired, be carried out inthe presence of a suitable diluent such as a naphtha or a suitable,preferably, volatile diluent, for one or both phases of the solventextraction, such as a volatile naphtha or non-volatile lube oil servingas diluent for the Product A phase, and methyl alcohol as a diluent forthe solvent phase.

It is particularly desirable to use as solvents compounds which containat least one aliphatic hydrocarbon group and at least one of theelements oxygen and nitrogen, particularly compounds in which the numberof oxygen atoms is at least one-half as great as the number of carbonatoms in the molecule, esters having given particularly favorableresults, especially the lower esters, such as ethyl acetate. I

The solvent extraction may be carried out under a fairly wide range oftemperature, such as between about room temperature and about 300 F.,but preferably the temperature should be about 150-250 F., and thepressure may be attop thereof and feeding the solvent, such as ethylacetate into the tower near the bottom thereof, the refined, i. e.substantially halogen-free Prodnot A being withdrawn continuously fromthe bottom of the tower, and withdrawing continuously from the top ofthe tower the ethyl acetate or other solvent containing dissolvedtherein the halogenated hydrocarbon liquid extracted from the raw orfresh Product A. The height of such a countercurrent extraction towershould preferably be at'least three times the diameter, and preferably 5to or or more times the diameter, and the solvent extract phase shouldpreferably be continuously separated into its several constituents, i.e. the solvent, halogenated hydrocarbon (extracted from the Product A)and hydrocarbon blend oil which may have been added to the Product Aprior to the extraction step, and the ethyl acetate or other extractionsolvent may be continuously recycled for further extraction.

In the normal course of preparation of the Product A, usingtetrachiorethane as the solvent, it is possible that the amount ofresidual chlorine in the Product A per se, free of blend oil may be ashigh as 10 to 15%, at least part of this chlorine being probablychemically combined in the prodnot, and by the use of a solventextraction according to this invention, this chlorine content may bereduced to less than 6% and preferably even less than 14%.

Although the preparation of the Product A per se does not constitutepart of the present invention, the following description of suchpreparation is given for the sake of illustration. The condensation ofchlorinated wax and naphthalene is carried out by using a chlorinatedwax having a chlorine content of at least 15%, and preferably to and anamount of aluminum chloride between the approximate limits of 0.5% and5.0%, with the important additional requirement that the arithmeticalproduct of the percent of catalyst, based on the weight of chlorinatedwax, times the square of the percent by weight of the chlorine in thechlorinated wax should be at least 400. Although the exact mechanism ofchemical reactions involved in this process is not well understood, itis believed that the success of the process depends to a substantialextent upon the use of a sufllcient amount of aluminum chloride catalystto cause proper reaction of the trichlorwax molecules in the chlorinatedwax use as raw material. Examination of chlorinate waxes containingvarious amounts of chlorine indicates that although there is a minorproportion of trichlor-product present with a major proportion of:monoand dichlor waxes in mixed products containing less than about 15%Cl, yet when mospheric or slightly above or below atmospheric,

the use of superatmospheric pressure being especially desirable if asolvent and/or diluent is used which has substantial volatility under.the temperature desired to be used. A reflux condenser may be used forvolatile solvents. The solvent extraction may be carried out by batchoperation,

using one or more stages, or may be carried out by continuous contactingof the Product A and solvent. The extraction may be carried out eitherconcurrently or countercurrently, and it is pref-' erable to use acontinuous countercurrent solvent extraction in suitable apparatus suchas avertical tower, which may optionally contain bailie plates 'orpacking material in order to increase the mix-j ing or contacting of theProduct A andsolveniaas by feeding the Product A into the tower near thethe chlorine content is 15% or above the relative proportion ofmonochlor and dichlor waxes decreases sharply with a correspondinglygreat \increase in the proportion. of trichlor wax so that inghlorinated waxes containing 15% or I over of chlorine the trichlor andhigher substituents are present in prepondering amount and atapproximately 20% Cl content there is about 75% of trichlor or highersubstituents present. when the chlorine content-reaches as high as 25%,there is relatively little monoor di-substituent'present.

In carrying out this condensation a large number of materials has beentested and found successful.

In the class of aromatic compounds, naphthalene has given outstandinglysuperior results and accordingly it is the preferred aromatic materialto be used. However, other aromatic compounds have given fairly goodresults, especially with control of reaction conditions such as by theuse of a relatively low proportion of solvent and a high proportion ofcatalyst, without, however, using very elevated temperatures unlessnecessary. Thus other aromatic compounds which may be used includebenzene, phenol, betanaphthol, diphenylene oxide, polymers ofdihydronaphthalene such as a tetramer thereof, and diphenyl, as well asother compounds analogous or equivalent thereto, as well as mixtures oftwo or more aromatic compounds, such, for instance, as found in coal tarfractions containing naphthalene, anthracene, and other polynucleararomatic hydrocarbons and derivatives thereof.

Instead of using chlorinated paraffln wax, one may also use otherhalogenated high molecular weight aliphatic materials, such aschlorinated petrolatum, chlorinated beeswax, and chlorinated derivativesof substantially saturated aliphatic hydrocarbon polymers, such aschlorinated polyethylene.

Although aluminum chloride is believed the best catalyst both from thepoint of view of cost and efllciency, other Friedel-Crafts catalysts maybe used if desirable, such as ferric chloride, titanium tetrachloride,boron chloride, or boron fluoride, or their mixtures.

The low molecular weight halogenated hydrocarbon solvent should be onewhich is inert un der the condensation reaction conditions used.Preferably it should be a chlorinated hydrocarbon having not more than 4carbon atoms and preferably containing 3 01' more chlorine atoms.Tetrachlorethane has been found to be especially suitable, althoughdichlorbenzene, trichlorethane, ethylene dichloride, trichlorbenzene,etc., may be used, if desired. Although this solvent does not actuallyenter into the chemical lene. On this same basis, when using 100 partsof chlorinated wax by weight, the aluminum chloride or other catalyst tobe used should be about 0.5 to 5.0%, or preferably about 1 to 3%.

V The amount of chlorinated hydrocarbon solvent to be used should beabout 10 to 200 volumes, or preferably to 100 volumes, for each 100volumes of chlorinated wax.

The reaction temperature should be maintained below 200' F,, except in afew particular instances where the aromatic compound is not veryreactive, and preferably should range from room temperature to 150 F.The reaction time may vary over a fairly wide range depending upon theamount of catalyst and solvent as well as the reaction temperature butnormally it dichloride, and neutralized or hydrolyzed by condensationreaction, nevertheless it has a defi nite influence on the course of thereactions because if a hydrocarbon solvent such as refined kerosene isused instead of chlorinated hydrocarbon solvent, in 'a condensationinvolving a chlorinated wax containing20% or more chlorine, theresulting condensation product will consist almost entirely ofa rubberyproduct which is completely insoluble in mineral oil.

Another important requirement for carrying out this condensation is theproper order of adding the ingredients, namely, the chlorinated wax mustbe added last in order to avoid formation of oil-insoluble condensationproducts when starting with chlorinated wax containing 20% or more ofchlorine.

The proportions of aromatic compound and chlorinated wax may be variedover a fairly wide range without seriously interfering with theproduction of the desired viscosity-index improving property. Forinstance, usually from 1-10-mols of chlorinated wax may be used for onemol of aromatic compound, preferably about 3-8 mols of chlorinated waxmay be used for one mol of aromatic compound. Since chlorinated wax isprobably the most important raw material and is generally used in largeamounts, one of the easiest ways to calculate the amount of various rawmaterials to be used is to base all calculations on 100 parts by weightor by volume of chlorinated wax and in such a case the amount ofaromatic compound to be used should range from about 5 to 30 parts byweight, or preferably about 10 to 15 parts in the case of napthaaddingwater or an aqueous solution of caustic soda, oraicohol or any suitablehydrolyzing agent or mixture of two or more of them. After the settlingand removal of the sludge layer, the reaction product is then subjectedto distillation, starting at either normal or reduced pressure, but inany case completing the distillation under substantially reducedpressure, such as by using fire and steam distillation or by vacuumdistillation, in order to obtain the desired high molecular weightdistillation residue, without causing any substantial cracking. Ifvacuum distillation is used, it may be controlled to an absolutepressure of between about 5 and millimeters ,of mercury, preferablyabout 10 to 50 millimeters. Usually, whether fire and steam distillationis used or vacuum distillation, the final temperature to which thedistillation is carried should be at least 350' F., and preferably atleast 400 F., and it may be 500 F. or 600 F.

A few tests indicate that a vacuum distillation under an absolutepressure of about 20 to 50 millimeters of mercury carried up to atemperature of 330 F. gave distillation results substantially equivalentto fire and steam distillation carried up to about 380 or 400 F. Ifdesired, the condensation product may be recovered as a blend in heavylubricating oil, by adding a small amount of a suitably high-boilingfraction to the reaction product just prior to or during thedistillation. This is preferable when it is desired to avoidredissolving the condensation product for use in lubricating oils.

The condensation product per se is a viscous liquid of approximatelyRobinson color with a green cast or bloom and soluble in hydrocarbonoils. As it undoubtedly is not all one single compound but is probably amixture of a number of different compounds having slightly differentstructure, the mixed product may, if desircd, be separated before orafter the chlorine-eliminating solvent extraction of this invention,into different fractions by various suitable means, such asdistillation, solvent extraction under other conditions, etc., in order'to recover one or more fractions which are especially potent in regardto viscosity-index improvement and/or pour depressing as well asoxidation-inhibiting and sludge-dispersing characteristics.

' The amount of addition agent to be used in it is desired to eflect asubstantial improvement in the viscosity index of the lubricating oilbase stock, which .may be paramnic, naphthenic.

mixed base. etc., but it may be used in considerably smaller amounts.such as 0.5%, 0.1%, 0.05% or even 0.01%, when it is desired to use thisaddition agent merely for pour-depressing in a parafllnic oil or for itsoxidation-inhibitin properties. An important advantage of thiscondensation product, especially in contrast to other productspreviously made from the same raw materials but under different reactionconditions is that it not only has good pour-depressing properties whenused in small amounts. such as 0.1% or 0.5%, butalso when used in verymuch larger amounts, such as 2% or as may be desirable when using it toimprove both viscosity index and pour point. Many previously known pourdepressors are effective only in amounts less than 1% or 2% and areeither ineffective or in some cases raise the pour point of thelubricating oil base stock when used in concentrations as large as 3%,5%, 7%. or

For the sake of illustrating the present invention, i. e., the improvedmethod of recovering Product A substantially free of residual halogen bysolvent extraction, the following examples are given.

Example 1 A sample of Product A was made from the following rawmaterials:

1 146 F. melting point paraflln wax having 21% C1.

The naphthalene and tetrachlorethane were first mixed in a flask andheated to 125 F., and then the AlCla was added (all at once). Then thechlor wax was fed into the reaction mixture in a small stream over aperiod of about 9 minutes, and the temperature of the reaction mixturewas held at 125 F. for a total of about 3 hours from the beginning ofthe addition of chlor wax. When the reaction was thus substantiallycompleted the reaction mixture was diluted with 800 ml. oftetrachlorethane and then neutralized with 500 ml. of aqueous isopropylalcohol (about 25 to 30% concentration). The mixture was stirred andthen allowed to settle overnight. The upper sludge layer was thenremoved and 600 grams of a paraflinic lubricating oil having a viscosityof about 43 seconds Saybolt at 210 F. and a V. I. (viscosity index) ofabout 100 was added to the solvent layer, which was then subjected tohigh vacuum distillation up to about 300 F. (the absolute pressure beingabout 10 mm. mercury). The distillation residue amounted to about 1150grams and therefore the yield of condensation product per se was 550grams (1150 minus the 600 grams of added blend oil) A small additionalamount of blend oil was added to make a blend having an even 40%concentration of Product A, the condensation product per se.

200 grams of the thus prepared 40% Product A blend, which analyzed 5.7%chlorine, indicating that the Product A per se contained 14.25% 01, wassuspended in 400 cc. of ethyl acetate in a suitable agitator andrefluxed with stirring for minutes. took place. The ester extract wasremoved and a fresh batch of 400 cc. of ethyl acetate added to theramnate. Befluxing and stirring for 15 minutes were repeated.

The ester extracts thus obtained were combined and distilled toremoveester, and to obtain as residue an oil phase containing 5.6%chlorine and weighing 142 grams was obtained. The blend Chlor wax I oilis per se completely miscible with ethyl acetate at room temperature, inall proportions. This means therefore that the ester extraction removedsubstantially' all or the 120 g. blend oil from the Product A blend butat the same time removed about 22 g. of Product A extract calculated tocontain about 36.14% C1 and therefore removed the major portion of themost highly chlorinated constituents.

The rafllnate obtained was exceedingly rubberyand viscous. To this wasadded 142 grams of fresh oil, in order to account for that portionremoved by the ester extraction, and the mixture was distilled to removethe ethyl acetate contained in the rafiinate phase. Analysis of thefinal product showed only 1.6% chlorine, which means a 70% removal ofchlorine from the Product A.

' Example 2 The above procedure was repeated except that acetone wasused as the solvent. A reduction of 51% in the chlorine content of theProduct A was obtained.

Example 3 The procedure of Example 1 was repeated except that secondaryamyl alcohol was used as solvent. A reduction of 47% in the chlorinecontent of the Product A was obtained. Another sample of polymer orcondensation product referred to as Product A was made from thefollowing raw materials:

Material Parts Na bthalene 13.5/wt. (70 grams). ISO/vol. (300 ml.).2.6/wt. (12 grams). /vol. (618 grams)-.-

117118 F. melting point paraffin wax having 22% Cl.

The naphthalene was first dissolved in the dichlor benzene, then theAlCls was added and the mixture warmed to about F. The chlor wax wasthen added over a 30-minute period during which the temperature rose toF. where it was held for 5 hours. The reaction mixture was then dilutedwith'more solvent (500 ml.), neutralized with a mixture of alcohol andwater, and settled. The aqueous layer was removed, and 300 grams of aparafilnic solvent extracted lubricating oil having a viscosity of 43seconds Saybolt at 210 F. was added to the solvent layer (to keep thecondensation product in solution) and the mixture was thendistilled withfire and steam to 550 F. The yield of distillation residue was 832 grams(which amounted to 64% by weight of polymer in the parafiinlc blendoil). This blend analyzed 5.2% 01. In order to make a polymerconcentrate containing only 40% polymer, 125 grams of the abovedescribed distillation residue (containing 64% of polymer) was blendedwith an additional 75 grams of paraflinic blend When cool, a separationof phases v 9 10 oil, thus making a 40% polymer blend which now' Inalyzed 3,2% Cl. 1 A. s. '1'. M. Pour Point, -1

Following the procedure in Example 1, 200 grams of this 40% polymerblend (80' grams Original E t t B m polymer in 120grams blend oil) weresuspended g gff fi fifi 3? in 400 cc.'o! ethyl acetate in a suitablevessel and the mixture was refluxed (at 175 F.) with stir- 30 30 ringfor 15 minutes. After cooling and settling2.15%1111111IIIIIIIIIIIIIIIIIII 35orbclow -5 38 overnight, a separationof phases tool: place. The Pi l y ester extract, was n d d t e Post oil:90 parafllnic oil of 442 sec. viscosity at 100 F. plus 10% volatileethyl acetate was removed by high Pennsylvania rightstwkvacuumdistillation to 220 F. 136 grams of fluid oil were recovered asdistillation residue, and since a number of different blends of ethylacetate The above viscosity index data show that the and th sam par flli ma s m 10 to raflinate blend is substantially as emcient in 5% c n nration were all mutually miscible concentration as the original polymerblend at room temperat t e t must have whereas the extract blend hasrelatively little viscontained the entire 120 grams of blend oil presityindex improving properties. The pour d ent in the original grams of P yblend pressing data show that the raflinate blend rebefore extraction,and therefore this extract con- 20 duced the S. pom-point from R totamed 16 grams o polymer extract D8 86 -30 F." when used in2.5%honcentration, and (136 grams minus 120 grams)- The mmhate this issubstantially as good as the original polyobta-med, which weighed 64grams (30 grams mer blend, whereas the extract blend only lowered minus16 grams) was then diluted with 136 grams pour m to 5 0! Dara-311116blend 011 to make a mmnate blend It is apparent therefore thatthesolvent extracweighing 200 grams, the same weig as that 01 tion ofthe present invention accomplishes a very the original Polymer blendbefore solvent extrac' substantial reduction in residual chlorinecontent oi the polymer condensation product with sub- Chlorihe analysesshwed that the Original stantially no loss in V. I. improving propertyand polymer blend contained 3.2% Cl (6.4 grams in pour depressingproperty the 200 gram sample) and therefore 8.0% C1 in For th k ofcomparison some experimental the Original polymer P while the data aregiven to show that products made acshowed 3.2% Cl (4.35 grams of C1) inthe extract cording to Patent 2,174,245 from the Same raw blend 273% C1based on the 16 grams of poly materials except that the chlorinatedparaflln wax mer extract Per and 12% C1 (2'34 grams of has a lowerchlorine content, and that less alumi- C1) in the 200 grams of finalraflinate blend, or num cmoride catalyst is n ral y suificient, have gfg the 64 grams of polymer mmnate good pour depressing properties buthave little or no viscosity index improving properties. In car- Thus inthis samplethe original waxnaph' rying out these tests, theprocedureused was the thalene polymer condensation product containing 0 same asdescribed in said patent test #1 herebe 8.0% Cl was divided by solventextraction into a low being substantially an exact duplicate of polymerextract containing 27.2% C1 and a poly ample VII of said patent, namelyusing a chlor mer rafllnate containing 35% wax having 15.2% chlorine andusing 1.4% AlCla. The three samples produced m the above as catalyst.Test #2 herebelow was made. by the scribed experiment namely theoriginal polymer same procedure except that the chlor wax used blend,the extract blend and the rafllnate blend, only contained 132% chlorineand 43% Alch was were added in small 9ncentmtions to parammc used ascatalyst. The following quantities of relube oils and were submitted toviscosity index actafits and solvent were used. and pour depressingtests with the .rol-lowing results:

Parts :by weight .Chlor wax 10o K j Naphthalene 13.5 9x22: i 118mmTetrachlorethane (solvent) 43 mend no end 136 Blend 195 ms grams grams116 116 116 The reaction was carried out at 125 F. for 3 g at hours.After recovery of the condensation high 133 1% 131 60 molecular weightproduct, it was added in small concentrations to lubricating oil andtested for pour depressing and viscosity index propertieslialsggorgltilgnsigysflgggg lubricating oil having a viscosity of withthe following results T heexents Pmdufit f fggfi) (aZii'r'fifii tm estNo.

' F158? Sitit'i. 835175; it-13 t. 15% 117% 215 i:

0 4 +30 +30 42,7 1.-.'.. 1.4 15.2 16 2, 082 -20 -1o 45. 106 2..., 4.013.2 as 1,319 --15 -5 45.7 106 ncl-ignition.

These tests showed that products made according to Patent 2,174,246 dohave good pour depressing properties, because they reduce the A. S. T.M. pour point of a waxy lube oil from +30 to -15 or --20 F. when used ina concentration as low as 0.15%, but they had substantially no viscosityindex improving properties because even when used in concentration theviscosity index of the oil was only changed from 100 to 106, whereasefiective V. I. improvers should produce about 3 or more times as greatan improvement.

In carrying out the solvent extraction of this invention it is desirableto use a volume of solvent equal to at least 50% and preferably about100 to 500 or 1000% of the volume of the Product A being treated. n

Also, if desired, one may add a small amount of a precipitant oranti-solvent, suchv as water or other suitable liquid serving tofacilitate the precipitation or separation of the-solvent Phase fr m theProduct A. I

By repeating the solvent xtraction a larger number of times, or bycarrying'out the solvent extraction in a continuous -counter-currentoperation, especially by the use of a relatively high vertical tower,and under optimum conditions of temperature, ratio 01' solvent toProduct A, etc.. a substantially larger amount of the residual chlorinemay be removed from the Product A than shown in the above examples. Ifdesired,

3. Process according to claim 1 in which the extraction solvent is aliquid organic compound containing at least one aliphatic hydrocarbongroup and containing at least one element selected from the groupconsisting oi! oxygen and nitrogen. I

4. Process according to claim 1 in which the extraction solvent is aliquid organic compound containing at least one aliphatic hydrocarbongroup and containing oxygen.

5. Process according to claim 1 in which the extraction solvent is anorganic liquid consisting of carbon, hydrogen, and oxygen, the number ofoxygen atoms being at least as great as one-half the number of thecarbon atoms.

6. Process according to claim 1 in which the extraction solvent is anester.

7. Process according to claim 1 in which the extraction solvent is ethylacetate.

8. Process according to claim 1 in which the solvent extraction iseffected by repeated batch extraction at about 150 F.-250 F.

9. Process according to claim 1 in which the solvent extraction iseflected by continuous countercurrent extraction in a vertical tower.

10. In the process of preparing high molecular weight condensationproducts by condensing a halogenated high molecular weight aliphaticmaterial having more than 10 carbon atoms and conone may use one type ofsolvent for one or more stages of solvent extraction and then use adiflerent type of solvent 'for one or more later stages, or run acontinuous counter-current extraction in one tower with one solvent andthen in another tower with another solvent.

This application is a continuation-in-part of application Ser. No.481,432, filed April 1, 1943 (now abandoned).

It is not intended that this invention be limited tothe specificexamples which have been given merely for the sake of illustration, butonly by the appended claims in which it is intended to claim allmodifications coming within the scope and spirit of the invention.

We claim:

1.. In the process of preparing high molecular weight condensationproducts by condensing a halogenated high molecular weight aliphaticmaterial having more than 10 carbon atoms and containing at least 15% ofhalogen, with an aromatic compound to make a higher molecular weightcondensation product, which comprises mixing together the aromaticcompound, about 0.5-5.0% of a Friedel-Crafts catalyst based on theweight of high molecular weight halogenated aliphatic material, and alow molecular weight halogenated hydrocarbon solvent inert under thereaction conditions, adding the halogenated high-molecular weightaliphatic hydrocarbon to the mixture of aromatic compound catalyst andsolvent, and maintaining the mixture at a reaction temperature until thereaction is completed, the arithmetical product of the percent ofcatalyst, based on the weight of halogenated high molecular weightaliphatic materiel, times the square of the percent by weight of halogenin the halogengated high molecular weight aliphatic material beingatleast 400, the improvement comprising extracting the condensationproduct, with a solvent for halogenated hydrocarbons to remove residualhalogenated hydrocarbon therefrom. a

2. Process according to claim 1 in which the extraction solvent is anorganic liquid containing hydrogen, carbon and at least one otherelement.

taining about 20 to of halogen, with an aromatic compound to make ahigher molecular weight condensation product, which comprises mixingtogether the aromatic compound, about 1 to 3% oi a Friedei-Craftscatalyst, based on the weight of hig'h molecular weight halogenatedaliphatic material and a low molecular weight halogenated hydrocarbonsolvent inert under the reaction conditions, adding the halogenated highmolecular weight aliphatic hydrocarbon to the mixture of aromaticcompound catalyst and solvent, and maintaining the mixture at a reactiontemperature until the reaction is completed, the arithmetical product ofthe percent of catalyst, based on the weight of halogenated highmolecular weight aliphatic material, times the square of the percent byweight of halogen in the halogenated high molecular weight aliphaticmaterial being at least 400, the improvement comprising extracting thecondensation product with a solvent consisting essentially of an organicliquid containing hydrogen, carbon and at least one other element.

11. The process of condensing a halogenated high molecular weightaliphatic material having more than 10 carbon atoms containing about 15to 30% of halogen, with an aromatic compound to make a higher molecularweight condensation product which comprises mixing together the aromaticcompound, about 0.55.0% of a Frledel- Crafts catalyst based on theweight of high molecular weight halogenated aliphatic material, "and alow molecular weight halogenated hydrocarbon solvent inert under thereaction conditions, adding the halogenated high molecular weightaliphatic hydrocarbon to the mixture of aromatic compound catalyst andsolvent, and maintaining the mixture at a reaction temperature until thereaction is completed, the arithmetical product of the percent ofcatalyst, based on the weight of halogenated high molecular weightaliphatic material, times the square of the alyst, subjecting thereaction product to'distillation under reduced pressure to obtain acondensation product substantially non-volatile up to at least 400 F.,and extracting said distillation residue with a solvent for halogenatedhydrocarbons to remove residual halogenated hydrocarbons therefrom, saidextraction solvent being a liquid organic compound containing hydrogen,carbon and at least one other element.

12. The process which comprises mixing together naphthalene, aluminumchloride and tetrachlorethane and adding thereto chlorinated paraflinwax containing about 25% chlorine, using about 3-8 mols of chlorinatedwax per mol of naphthalene, about 1-3% of aluminum chloride based on theweight of the chlorinated wax and about 20-100 volumes oftetrachlorethane per 100 volumes of chlorinated wax, and maintaining thereaction mixture at a temperature between the approximate limits of70-150 F. for a reaction time of about /4. to 5 hours, treating thereaction mixture with a hydrolyzing agent, settling and removing thecatalyst sludge therefrom, distilling the reaction products underreduced pressure to a temperature of at least 400 F. to obtain a highmolecular weight wax-naphthalene condensation ADOYSIUS F. cAsHMAn.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,339,493 Lieber et a1 Jan. 18,1944 2,297,292 Davis et al. Sept. 29, 1942 2,030,307 McLaren Feb. 11,1936

